3-benzylidene-camphors, process for their preparation and their use in protection against UV rays

ABSTRACT

The invention relates to new 3-benzylidene-camphor derivatives of the formula: ##STR1## in which R 1  denotes H or SO 3 .sup.⊖ M.sup.⊕, with M=H, an alkali metal or N.sup.⊕ (R 3 ) 4 , with R 3  =H or C 1  -C 4  alkyl or hydroxyalkyl; R 2  denotes C 1  -C 4  alkyl or C 1  -C 4  alkoxy and n=0-4; and Z denotes ##STR2## in which R 4  has the same meaning as R 1  and can be identical or different, or alternatively ##STR3## in which R 5  denotes H, optionally substituted aryl, C 1  -C 4  alkyl, --CN, --C00R7 or ##STR4## and R 6  denotes --COOR 8  or ##STR5## in which R 7  and R 8 , which are identical or different, denote alkyl, alkenyl, cycloalkyl or aralkyl and R 9  and R 10 , which are identical or different, denote H, alkyl, alkenyl or cycloalkyl; if R 5  =H, alkyl or aryl, R 6  can represent --COO.sup.⊖ M.sup.⊕ ; the methylidene-camphor radical, on the one hand, and the radical Z, on the other hand, are in the meta or para position. These derivatives act as sun filters.

This is a divisional of application Ser. No. 505,090 filed June 16,1983, now U.S. Pat. No. 4,585,597.

The present invention relates to compounds derived from3-benzylidene-camphor, to a process for their preparation and to theiruse in protection against ultraviolet radiation in the cosmetics field.

It is known that light radiation with wavelengths of between 280 and 400nm makes it possible to brown the human epidermis and that rays withwavelengths of between 280 and 320 nm, known by the name UV-B can alsocause erythema and skin burns, which can hinder the development of atan.

It is already known to use compounds which are active in theabovementioned wavelength range of 280-320 nm. U.S. Pat. No. 3,781,417describes 3-(4'-methylbenzylidene)-camphor, the absorption maximum ofwhich is at 297 nm, as a UV-B absorber. This compound has goodsolubility in oils, but is insoluble in water.

Other benzylidene-camphor derivatives are also known for possessingabsorption properties in the wavelength range of 280-320 nm. Theseinclude brenzylidene-camphor derivatives containing a quaternaryammonium radical on the benzene nucleus, in the para position relativeto the bornylidene radical, according to French Pat. No. 2,199,971,benzylidene-camphor derivatives sulphonated on the methyl radical in the10-position of the camphor or in the 3'-position or 4'-position on thebenzene nucleus, according to French Pat. Nos. 2,282,426 and 2,236,515,and p-methylbenzylidene-camphor derivatives substituted on the p-methylgroup, according to French Pat. Nos. 2,383,904, 2,402,647 and 2,421,878.

However, although the UV-B rays with wavelengths of between 280 and 320nm play a predominant part in the production of solar erythema and mustbe filtered out, it is no less true that the UV-A rays, with wavelengthsof between 320 and 400 nm, which cause the skin to brown, also damagethe skin, in particular in the case of a sensitive skin or a skincontinually exposed to solar radiation. It has been found that the UV-Arays can potentiate the action of the UV-B rays, as has been describedby several groups of authors and more particularly by J. Willis, A.Kligman and J. Epstein (The Journal of Investigative Dermatology, Volume59, No. 6, page 416, 1973) under the name Photo-enhancement. The UV-Arays favour the initiation of the erythematous reaction or increase thisreaction in certain subjects. Likewise, they can be the cause ofphototoxic or photoallergic reactions.

Attempts have therefore been made to find compounds which absorb the UVrays strongly over a wide band; and compounds absorbing the UV rays withwavelengths of between 315 and 340 nm, in particular, have beendiscovered, such as 3-para-hydroxybenzylidene-bornan-2-ones of FrenchPatent Application No. 2,430,938 or 3-cinnamylidene-camphor of U.S. Pat.No. 3,781,417.

Furthermore, it is known that the constituents present in cosmeticpreparations, and in particular certain dyestuffs in dyeingcompositions, coloured hair lacquers, shampoos, setting lotions andmake-up products such as tinted creams, nail varnishes and lipsticks, donot always possess sufficient light stability, and that they degradeunder the action of light radiation.

Consequently, it is desirable to have available a group of compoundscapable of absorbing both the UV-A rays and the UV-B rays, and to beable to protect the various products sensitive to this radiation byincorporating such agents which filter out the UV-A and UV-B rays intothe products, preparations and compositions sensitive to this radiation.

We have discovered that, surprisingly, certain 3-benzylidene-camphorderivatives have good filtering properties with respect to UV-A and UV-Brays, are soluble in the customary cosmetic solvents and have good heatstability and excellent photochemical stability.

The present invention therefore provides 3-benzylidene-camphors of thegeneral formula: ##STR6## in which R₁ denotes a hydrogen atom or aradical --SO₃ ⁻ M⁺, in which M denotes a hydrogen atom, an alkali metalor a group N(R₃)₄ ⁺, R₃ denoting a hydrogen atom or a C₁ to C₄ alkyl orhydroxyalkyl radical, R₂ denotes a linear or branched C₁ to C₄ alkylradical or a C₁ to C₄ alkoxy radical, n being 0 or an integer from 1 to4; and when n is 2 or more R₂ radicals can be the same or different; andZ represents a group in which R₄ has the same meanings as R₁ and can beidentical to R₁ or different from R₁, or alternatively a group ##STR7##in which R₅ denotes a hydrogen atom, a C₁ to C₄ alkyl radical, an arylradical optionally substituted by one or more halogen atoms or by C₁ toC₄ alkyl or alkoxy groups, or a radical --CN, --COOR₇ or ##STR8## and R₆denotes a group --COOR₈ or ##STR9## R₇ and R₈, which are identical ordifferent, being alkyl, alkenyl, cycloalkyl or aralkyl radicalscontaining up to 20 carbon atoms, which are optionally substituted byone or more hydroxyl, alkoxy, amine or quaternary ammonium groups, andR₉ and R₁₀, which are identical or different, denoting a hydrogen atomor alkyl, alkenyl, cycloalkyl or aralkyl radicals containing up to 20carbon atoms, which are optionally substituted by one or more hydroxyl,alkoxy, amine or quaternary ammonium groups, or alternatively, if R₅denotes a hydrogen atom, an alkyl radical or an optionally substitutedaryl radical, R₆ can also represent a radical --COO.sup.⊖ M.sup.⊕, Mbeing defined as above, the methylidene-camphor radical, on the onehand, and the radical Z, on the other hand, being attached to thearomatic nucleus A either in the meta position or in the para positionrelative to one another.

The following radicals may be mentioned amongst the preferred radicalsR₇, R₈, R₉ and R₁₀ : ethyl, propyl, butyl, hexyl, 2-ethylhexyl, menthyl,oleyl, benzyl and 4-methoxybenzyl, and the phenyl radical may bementioned amongst the preferred aryl radicals for R₅.

Depending on the nature of the substituents R₁, R₂, R₄, R₅ and R₆, thecompounds of the formula (I) can be water-soluble or liposoluble.

If Z represents a group ##STR10## and if R₆ is different from--COO.sup.⊖ M.sup.⊕, R₁ is preferably a hydrogen atom; these compoundsare generally lipophilic.

The compounds of the formula (I) have molar absorption coefficients (ε)which are generally high, generally above 30,000 at between 300 and 380nm.

The position of the absorption maxima for the compounds of the formula(I) depends on the nature of R₂ and also on the relative position of themethylene-camphor radical, and the radical Z to one another and also tothe group(s) R₂ when the latter are electron donors.

In general, the products in which the methylidene-camphor radical andthe radical Z are in the para position absorb at wavelengths higher thanthose at which the corresponding meta-substituted products absorb.

According to the invention, a wide range of compounds is thereforeavailable, constituting sun filters which filter out both the UV-A raysand the UV-B rays.

The present invention also provides a process for the preparation of thecompounds of the formula (I).

The compounds of the formula (I) can be obtained by the followingprocesses, which differ according to whether the compounds aresymmetrical or asymmetrical.

1--Process for the preparation of the symmetrical compounds of theformula (I) in which Z= ##STR11## and R₁ =R₄ ##STR12##

This type of reaction can be carried out in an anhydrous solvent, whichis preferably aprotic, in the presence of an organic base such as analkali metal alcoholate, or of a inorganic base such as an alkali metalamide or hydride, the water formed being removed. In certain cases, itis also possible to carry out the reaction in a water-immisciblesolvent, in the presence of aqueous solutions of sodium hydroxide orpotassium hydroxide.

2--General process for the preparation of the symmetrical andasymmetrical compounds

(a) Z= ##STR13## R₄ being identical to R₁ or different from R₁.##STR14##

The reaction can be carried out under conditions identical to thosedescribed for process (1).

(b) Z= ##STR15##

The reaction scheme used is as follows: ##STR16## It corresponds to theconventional formation of a cinnamic acid derivative from an aromaticaldehyde.

The preferred compounds (I) according to the invention are the compoundsin which Z is in the para position, the majority of which constitute sunfilters which filter out the UV-A radiation, that is to say filtershaving an absorption maximum above or equal to 320 nm.

These compounds desirably have the formula: ##STR17##

The compounds of the formula (II) in which Z is in the para position)have very good solubility in water or oils, depending on the nature ofthe substituents.

Of course, the compounds of the formula (I) or (II) can give rise to"cis-trans" isomerism around one or more double bonds, and all theisomers form part of the present invention.

The compounds of the formula (I) or (II) according to the invention arefurther illustrated by Examples (1) to (23) which follow, and thecharacteristics of these compounds: preparative procedure, meltingpoint, wavelength corresponding to the absorption maximum (λ)_(max),molar absorption coefficient (ε) and analysis, are indicated in thetable below.

      ##STR18##       Example R.sub.1 n, R.sub.2 Z Preparative procedure Melting point UV     absorption λmax. (ε) Analysis               1 H O      ##STR19##      A 258° C. 347 nm (CHCl.sub.3)(ε = 35,000) Theory:        H     C:69.68:7.10 S:6.64Found:C:69.96H:7.07 S:6.59    in the para position  2     H O      ##STR20##      A -- 342 nm (CHCl.sub.3) (ε = 39,600) --    in the para     position      3 H O     ##STR21##      C oil 328 nm (EtOH)(ε =      39,000) Theory: C:76.77 H:9.40Found:C:76.76 H:9.34    in the para     position      4 H O     ##STR22##      B 227° C. 327 nm (EtOH)(ε = 41,000) Acid number:Theory:     3.22 meq/gFound:3.28 meq/g    in the para position      5 H O     ##STR23##      D 132° C. 350 nm (CHCl.sub.3)(ε = 50,000) Theory:        H     C:76.01:6.93 N:3.85Found:C:75.98H:6.88 N:3.73    in the para position  6     H O      ##STR24##      A 234° C.. 337 nm (CHCl.sub.3) (ε = 38,700) Theory:     C:83.54H:8.51 O:7.95Found:C:83.54H:8.56 O:7.91    in the para position     7 H O      ##STR25##      C 84° C. 335 nm (CHCl.sub.3)(ε = 39,500) Theory: C:73.15     H:7.37Found:C:73.06 H:7.30    in the para position      8 H O CHCHCO.sub.2(CH.sub.2 ).sub.3CH.sub.3 B + E 80° C. 331 nm     (CHCl.sub.3) Theory: C:78.65 H:8.25    in the para position   (ε     = 43,500) Found:C:78.75 H:8.24      9 H O     ##STR26##      D 83° C. 355 nm (CHCl.sub.3)(ε = 39,000) Theory:     C:77.82H:8.33 N:3.13Found:C:77.83H:8.28 N:3.12    in the para position     10 H n = 4R.sub.2 =      CH.sub.3     ##STR27##      F 270° C. 290 nm (CHCl.sub.3)(ε = 12,500) Theory:     C:83.79 H:9.23Found:C:83.59 H:9.24    in the para position  11 H O      ##STR28##      C <55° C. 332 nm (CHCl.sub.3)(ε = 39,000) Theory:     C:78.05 H:9.27Found:C:78.01 H:9.29    in the para position  12 H O     CHCHCONH2-ethylhexyl B + G + H <55° C. 328 nm (CHCl.sub.3)     Theory: C:79.76    in the para position   (ε = 47,000) H:9.32     N:3.32        Found:C:79.69        H:9.35 N:3.25      13 H O     ##STR29##      B + G + I 144° C. 328 nm (CHCl.sub.3)(ε =  47,800)     Theory: C:78.11 H:7.02Found:C:78.35 H:7.06    in the para position  14 H     O      ##STR30##      J 152° C. 295 nm (CHCl.sub.3)(ε = 41,500) Theory:     C:83.54 H:8.51Found:C:83.48 H:8.50    in the meta position  15 H O     CHCHCOO(CH.sub.2).sub.8CH B + K oil 329 nm (EtOH) Theory: C:81.38     H:10.08    CH(CH.sub.2).sub.7CH.sub.3   (ε =      36,100) Found:C:81.16 H:10.19    in the para position      16 H O     ##STR31##      A Softening point134° C. 208 nm (water)(ε = 37,000) Acid     number:Theory: 2.07 meq/gFound:1.98 meq/g    in the meta position  17 H     O      ##STR32##      L 238° C. 334 nm (EtOH)(ε = 32,750) Acid number:Theory:     2.59 meq/gFound: 2.56 meq/g    in the para position      18 H O     ##STR33##      L + M 86° C. 335 nm (EtOH)(ε = 40,000) Theory: C:81.66     H:8.14Found:C:81.34 H:8.27    in the para position  19 SO.sub.3 H O      ##STR34##      N 255° C. with decomposition 342 nm (H.sub.2 O)(ε =     42,300) Theory: C:56.18 H:6.35O:26.76 S:10.70Found:C:55.92 H:6.40O:26.17     S:10.88    in the para position  20 SO.sub.3.sup.⊖ Na.sup.⊕     O      ##STR35##      N -- 345 nm (H.sub.2 O)(ε = 44,000) --    in the para position     21 SO.sub.3.sup.⊖ N.sup.⊕ H(CH.sub.2 CH.sub.2 OH).sub.3 O      ##STR36##      N -- 345 nm (H.sub.2 O)(ε = 40,000) --    in the para position     22 H O      ##STR37##      O -106° C. 323 nm (EtOH)(ε = 37,360) Theory: C:78.37     H:8.01Found:C:78.35 H:8.02    in the para position  23 H O CHCHCH.sub.2     ethyl P 85.5° C. 283 nm (EtOH) Theory: C:78.07 H:7.74    in the     para position   (ε =      45,300) Found: C:78.04 H:7.72

The procedures (A) to (P) used to prepare the compounds (1) to (23) areset out below.

PROCEDURE A

134 g of 4'-formyl-3-benzylidene-camphor, 1,350 ml of dry toluene, 116 gof camphosulphonic acid and 22 g of sodium hydroxide pellets are placedin an equipped 3 liter three-necked round-bottomed flask. The mixture isheated under reflux for 1 hour, the water formed being separated offwith the aid of a Dean-Stark apparatus (18 ml). The solution is cooledand poured into 3 liters of isopropyl ether. The precipitate is filteredoff, washed with isopropyl ether and dried.

The compound obtained is dissolved in 2 liters of hot acetone and thesolution is acidified with 25 ml of concentrated hydrochloric acid. Theinorganic salts which precipitate are filtered off and the filtrate isevaporated to dryness. The residue is taken up in 1 liter of isopropylether, filtered off and dried in vacuo. This gives 191 g of compound (1)(yield=79%).

Compound (2) is obtained by neutralising an aqueous solution of compound(1) with triethanolamine used stoichiometric proportions. The aqueoussolution is lyophilised to remove the water and to give the compound inpowder form.

Procedure A is also used to prepare compound (6), the camphosulphonicacid being replaced by camphor, and to prepare compound (16), the4'-formyl-3-benzylidene-camphor being replaced by3'-formyl-3-benzylidene-camphor.

PROCEDURE B

22 g of malonic acid and 40 ml of dry pyridine are placed in an equipped250 ml round-bottomed flask. The mixture is stirred until dissolution iscomplete. 1 ml of piperidine is then added, followed by 27 g of4'-formyl-3-benzylidene-camphor, and the whole is heated gradually to110° C. Gas is evolved and this stops after a heating time of about 1hour 30 minutes.

The solution is then cooled and acidified by adding 100 ml of 6Nhydrochloric acid. The precipitate formed is filtered off, washed withwater until the washings are neutral, and dried in vacuo.

This gives 30 g of compound (4) (yield=96%).

PROCEDURE C

69 g of 2-ethylhexyl malonate, 2 ml of piperidine, 500 ml of ethanol and54 g of 4'-formyl-3-benzylidene-camphor are placed in an equipped 1liter round-bottomed flask.

The mixture is heated under reflux for 24 hours. A further 2 ml ofpiperidine are then added and the mixture is heated under reflux for 6hours.

The solution is cooled and concentrated in vacuo. The residue is takenup in 500 ml of toluene. The organic phase is washed several times withwater, dried and concentrated in vacuo.

The oil obtained is chromatographed on silica (eluant: acetone/hexane(1/9)).

This gives 55 g of compound (3) (yield: 47%).

To prepare compounds (7) and (11), the 2-ethylhexyl malonate is replacedby ethyl malonate and menthyl malonate respectively.

PROCEDURE D

10.6 ml of ethyl cyanoacetate, 50 ml of absolute ethanol and 1.5 g ofpotassium fluoride, as a catalyst, are placed in an equipped 250 mlround-bottomed flask.

27 g of 4'-formyl-3-benzylidene-camphor are added to this mixture insmall portions. The reaction mixture becomes pasty, 125 ml of absoluteethanol are then introduced and the mixture is stirred at 50° C. for 1hour.

The mixture is cooled and the precipitate is filtered off, washed with200 ml of ethanol and then with 200 ml of water and finally dried invacuo.

This gives 32.7 g of compound (5) (yield: 90%).

To obtain compound (9), the ethyl cyanoacetate is replaced by2'-ethylhexyl cyanoacetate.

PROCEDURE E

56 g of p-(2-oxo-3-bornylidene-methyl)-cinnamic acid (compound 4), 27 gof butanol, 800 ml of dry benzene and 4 ml of concentrated sulphuricacid are placed in an equipped 2 liter reactor.

The mixture is heated under reflux for 4 hours, the water formed beingseparated off with the aid of a Dean-Stark apparatus.

The solution is then cooled and subsequently washed with water, driedand evaporated to dryness.

The residue is recrystallized from ethanol.

This gives 70 g of compound (8) (yield=76%).

PROCEDURE F

40 g of camphor, 200 ml of dry toluene, 23 g oftetramethylterephthaldehyde and 9.6 g of sodium hydroxide pellets areplaced in an equipped 1 liter reactor.

The mixture is heated under reflux for 96 hours, the water formed beingseparated off.

The organic phase is then washed with water, dried and concentrated invacuo.

The residue is taken up in 500 ml of toluene and filtered off on silica.The solution is evaporated to dryness. This gives 21 g of compound (10)(yield=38%).

PROCEDURE G

31 g of p-(2-oxo-3-bornylidene-methyl)-cinnamic acid (compound 4), 200ml of dry toluene and 24 g of thionyl chloride are placed in an equipped500 ml reactor.

The mixture is heated under reflux for 2 hours. The excess thionylchloride is driven off and the toluene is then distilled in vacuo.

The residue is recrystallised from a 40/60 toluene/hexane mixture.

After drying, 26 g of p-(2-oxo-3-bornylidene-methyl)-cinnamoyl chlorideare obtained (yield=80%).

PROCEDURE H

10 g of the acid chloride obtained under G, 3.9 g of 2-ethylhexylamine,4.2 ml of triethylamine and 100 ml of methylene chloride are placed inan equipped 250 ml round-bottomed flask.

The mixture is heated under reflux for 2 hours. After cooling, theorganic phase is washed with water, dried and filtered and the filtrateis concentrated to dryness.

The oily residue is dried in vacuo to give an amorphous solid.

This gives 12.2 g of compound (12) (yield=96%).

PROCEDURE I

4.15 g of p-methoxybenzyl alcohol and 20 ml of pyridine are placed in anequipped 100 ml round-bottomed flask, and 9.9 g of the acid chlorideobtained under G are introduced in small portions at ambienttemperature.

The reaction is slightly exothermic.

When the addition has ended, the mixture is heated at 70° C. for 1 hour.

After cooling, the solution is poured into a mixture of 200 ml of iceand 30 ml of concentrated hydrochloric acid.

The precipitate formed is filtered off, washed with water andrecrystallised from acetone. This gives 6.8 g of compound (13)(yield=52%).

PROCEDURE J

25 g of potassium tert.-butylate and 250 ml of toluene are placed in anequipped one liter reactor, and 33.5 g of camphor are then introduced insmall portions.

The reaction is exothermic (maximum temperature 60° C.).

After the mixture has cooled to 40° C., a solution of 13.4 g ofisophthaldehyde in 200 ml of dry toluene is introduced dropwise.

The mixture is then heated under reflux for about 4 hours andsubsequently poured into 700 ml of ice containing 25 ml of concentratedhydrochloric acid. The solid formed is filtered off (isophthalic acid)and the filtrate is left to separate.

The organic phase is separated off, dried and concentrated in vacuo. Theoily residue is chromatographed on a silica column (eluant=methylenechloride). This gives 10 g of compound (14).

PROCEDURE K

300 ml of dry benzene, 200 ml of dry toluene, 228 g of oleyl alcohol,3.2 ml of concentrated sulphuric acid and then 45 g ofp-(2-oxo-3-bornylidene-methyl)-cinnamic acid (compound 4) are placed inan equipped 2 liter reactor.

The mixture is heated under reflux for 5 hours, the water formed beingseparated off with the aid of a Dean-Stark apparatus.

The solution is then cooled and is subsequently washed with water, driedand evaporated to dryness. The residue is subjected to distillationunder 0.1 mm Hg at 160°-174° C. in order to remove the excess oleylalcohol. The expected ester is isolated by column chromatography in thepresence of silica gel and chloroform (10 liters of CHCl₃ +2 kg ofsilica gel).

The chloroform part, containing the oleylp-(2-oxo-3-bornylidene-methyl)-cinnamate, is concentrated to give 40 gof compound (15) (yield 40%).

PROCEDURE L

A mixture containing 17.4 g (0.1 mol) of potassium phenylacetate, 5 g(0.035 mol) of potassium carbonate, 0.5 ml of pyridine, 26.8 g (0.1 mol)of 4'-formyl-3-benzylidene-camphor and 15.3 g (0.15 mol) of aceticanhydride is heated for 2 hours at 180°-190° C. A stream of nitrogen ismaintained throughout the heating period.

After cooling, 300 ml of ice and then 50 ml of 6N potassium hydroxidesolution are added. Extraction is carried out with 50 ml of ether andthe aqueous phase is then acidified. The precipitate is recrystallizedfrom 100 ml of 50% strength ethyl alcohol. This gives 15.2 g of compound(17).

PROCEDURE M

A solution of 7.72 g (0.02 mol) of compound (17) obtained by procedureL, 5 ml of hexanol, 50 ml of toluene and 3 drops of concentratedsulphuric acid is heated under reflux in a round-bottomed flask equippedwith a Dean-Stark apparatus.

After 3 hours under reflux, the reaction mixture is concentrated. Theresidue is recrystallized from ethanol. This gives 5.9 g of pale yellowproduct (18).

PROCEDURE N

223 g (2 mols) of 97% strength sodium methylate are added to asuspension of 464.8 g (2 mols) of 10-d,l-camphosulphonic acid in 4liters of toluene and 0.2 liter of methanol, and the mixture is thenheated under reflux for 30 minutes.

A solution of 134.2 g (1 mol) of terephthalaldehyde in 1 liter of a90/10 toluene/methanol mixture is then added in the course of 2 hours,under nitrogen. The mixture is kept under reflux for 1 hour and thencooled to ambient temperature.

The toluene is drawn off and the product is taken up in 1.5 liters ofwater and 1.5 liters of 35% strength hydrochloric acid. The mixture isheated under reflux for 1 hour, the residual toluene being distilled.

After the medium has been concentrated and cooled, the concentrate isfiltered and the material on the filter is washed with 6N hydrochloricacid and dried in vacuo at 80° C. and then at 100° C. This gives 395 gof compound (19).

This is dissolved in water, the stoichiometric amount of sodiumcarbonate is added and the sodium disulphonate, which precipitates, iseasily obtained. After dilution with acetone, filtration and drying invacuo at 80° C. and then at 100° C., the sodium disulphonate (20) isobtained with a virtually quantitative yield.

The triethanolamine salt (21) is obtained in the same way from compound(19) by using a stoichiometric amount of triethanolamine.

PROCEDURE O

5 ml (10⁻² mol) of ethyl 2-diethylphosphonopropionate, 5.4 g of4'-formyl-3-benzylidene-camphor 2.10⁻² mol), 40 ml of a saturatedsolution of potassium carbonate and 40 ml of water are introduced into a250 ml round-bottomed flask. After vigorous stirring for 24 hours atambient temperature, extraction is carried out with 3 times 50 ml oftoluene. The organic phase is washed with water, distilled, dried andthen evaporated to give 8 g of a yellowish oil, which crystallises inthe cold. The product is recrystallized from hexane, which gives 5.2 gof white crystals of compound (22).

PROCEDURE P

A suspension of 1 g of powdered potassium hydroxide in 30 ml of dioxaneis placed in a 100 ml round-bottomed flask. A solution of 1.12 g (5.10⁻³mol) of ethyl diethyl-phosphonoacetate and 1.34 g of3'-formyl-3-benzylidene-camphor (5.10⁻³ mol) in 30 ml of dioxane isadded dropwise. After stirring for 1 hour, the reaction medium isdiluted with 40 ml of toluene. Filtration and evaporation of thesolvents gives an oil, which crystallises in the cold. Afterrecrystallisation from hexane, a product which melts at 85.5° C. (23) isobtained.

The present invention also provides a cosmetic composition containing atleast one 3-benzylidene-camphor derivative of the formula (I) accordingto the invention, as an agent for protection against ultraviolet rays,in a cosmetically acceptable medium.

If it is used as a composition intended for protecting the humanepidermis against ultraviolet rays, the cosmetic composition accordingto the invention can be presented in the widest variety of formsnormally used for this type of composition. It can be, in particular, inthe form of a solution, a lotion, an emulsion such as a cream or a milk,an aqueous-alcoholic or alcoholic gel or a solid stick, or can bepackaged in an aerosol.

It can contain the cosmetic adjuvants normally used in this type ofcomposition, such as thickeners, softeners, humectants, superfattingagents, emollients, wetting agents, surface-active agents,preservatives, anti-foam agents, perfumes, oils, waxes, dyestuffs and/orpigments serving to colour the composition itself or the skin,bactericides or any other ingredient normally used in cosmetics.

The compound of the formula (I) is suitably present in proportions byweight of 0.5 to 15%, relative to the total weight of the composition.

Solubilisation solvents which can be used include a lower monoalcohol orpolyol or a mixture thereof, or an aqueous-alcoholic solution. Theparticularly preferred monoalcohols or polyols are ethanol, isopropanol,propylene glycol and glycerol.

One embodiment of the invention is an emulsion in the form of aprotective cream or milk comprising, in addition to a compound of theformula (I), at least one fatty alcohol, oxyethyleneated fatty alcoholor fatty acid ester, and, in particular, a fatty acid triglyceride, afatty acid, lanoline, a natural or synthetic oil, or a wax, in thepresence of water.

Another embodiment consists of lotions such as oily-alcoholic lotionsbased on a lower alcohol such as ethanol, or on a glycol such aspropylene glycol, and/or on a polyol such as glycerol, and on a fattyacid ester such as a fatty acid triglyceride.

The cosmetic composition of the invention can also be anaqueous-alcoholic gel comprising one or more lower alcohols such asethanol, propylene glycol or glycerol, and a thickener, in the presenceof water.

The present invention also provides anti-sunburn cosmetic compositionscontaining at least one compound of the formula (I), which can beassociated with other sun filters specific for UV-B radiation and/orUV-A radiation, which are compatible with the compounds according to theinvention. It is thus possible to obtain a formulation which filters outall the UV-B and UV-A radiation.

The compounds according to the invention can be associated with UV-Bfilters which can be liposoluble compounds or oils having filteringproperties, in particular coffee bean oil. Lipophilic UV-B sun filterswhich may be mentioned include salicyclic acid derivatives such as2-ethylhexyl salicylate and homomenthyl salicylate, cinnamic acidderivatives such as 2-ethylhexyl p-methoxycinnamate and 2-ethoxyethylp-methoxycinnamate, p-aminobenzoic acid derivatives such as amylp-aminobenzoate and 2-ethylhexyl p-dimethylamino-benzoate, benzophenonederivatives such as 2-hydroxy-2-methoxybenzophenone and2,2'-dihydroxy-4-methoxy-benzophenone, and camphor derivatives such as3-(4-methylbenzylidene)-camphor, optionally associated with4-isopropyldibenzoylmethane or 3-benzylidene-camphor.

As water-soluble sun filters which filter out the UV-B rays and whichcan also be associated with the liposoluble or water-soluble filters ofthe invention, provided that they are compatible with the latter, theremay be mentioned the benzylidene-camphor derivatives described in FrenchPat. Nos. 2,199,971, 2,236,515, 2,383,904, and, more particularly,4-(2-oxo-3-bornylidene-methyl)-phenyltrimethylammonium methylsulphateand salts of 4-(2-oxo-3-bornylidene-methyl)-benzenesulphonic acid, of2-methyl-5-(2-oxo-3-bornylidene-methyl)-benzenesulphonic acid and of2-phenylbenzimidazole-5-sulphonic acid.

The compounds according to the invention can also be associated withUV-A filters, amongst which dibenzoylmethane derivatives may bementioned.

It is to be understood that the list of sun filters which can be used inassociation with the compounds (I) according to the invention is notexhaustive.

The anti-sunburn compositions according to the invention can bepresented in the form of, for example, solutions, lotions, emulsionssuch as a cream or a milk, oils, fatty gels or aqueous-alcoholic oralcoholic gels, or can be packaged in an aerosol or as solid sticks.They can contain the abovementioned cosmetic adjuvants normally used inthis type of composition.

The present invention also provides coloured or non-coloured cosmeticcompositions containing at least one compound of the formula (I) as anagent for protection against ultraviolet rays.

These compositions may be in the form of, for example, hair compositionssuch as hair lacquers, setting lotions, which optionally have a treatingor disentangling function, shampoos, colouring shampoos and hair dyeingcompositions, make-up products such as nail varnishes, epidermistreatment creams, make-up foundations and lipsticks, and any othercosmetic composition which, by virtue of its constituents, can presentproblems of light stability during storage.

The invention also provides a process for protecting the human epidermisagainst UV-A rays and UV-B rays, which consists in applying, to theskin, at least one compound of the formula (I) in a cosmeticallyacceptable medium and optionally associated with other agents whichabsorb UV-A and/or UV-B rays.

The invention also provides a process for protecting coloured cosmeticcompositions against UV-A and UV-B rays, which consists in incorporatingat least one compound of the formula (I) into these compositions.

The present invention is further illustrated by the followingapplication Examples.

EXAMPLE 24

    ______________________________________                                        Protecting day cream                                                          ______________________________________                                        Compound of Example 7    1      g                                             Polyoxyethyleneated fatty alcohols                                                                     7      g                                             Fatty acid triglycerides 30     g                                             Glycerol monostearate    2      g                                             Silicone oil             1.5    g                                             Cetyl alcohol            1.5    g                                             Preservatives            0.3    g                                             Perfume                  0.6    g                                             Demineralised water q.s.p.                                                                             100    g                                             ______________________________________                                    

To prepare this cream, the fatty substances are heated to about 80°-85°C.; the filter of the formula (I) is added. The water is heatedseparately to 80°-85° C. and the fatty phase is added to the aqueousphase with vigorous stirring; the stirring is maintained for 10 to 15minutes and the mixture is then left to cool, with moderate stirring,and the perfume is added at about 40° C.

EXAMPLE 25

    ______________________________________                                        Protecting day cream                                                          ______________________________________                                        Compound of Example 6    0.5    g                                             Benzylidene-camphor      0.5    g                                             Triglycerides of C.sub.8 to C.sub.12 fatty acids                                                       31     g                                             Glycerol monostearate    6      g                                             Stearic acid             2      g                                             Cetyl alcohol            1.2    g                                             Lanoline                 4      g                                             Preservatives            0.3    g                                             Propanediol              2      g                                             Triethanolamine          0.5    g                                             Perfume                  0.5    g                                             Demineralised water q.s.p.                                                                             100    g                                             ______________________________________                                    

The fatty substances are heated to about 80°-85° C. and the filters areadded; with vigorous stirring, the fatty phase is added to the water(containing the water-soluble compounds) heated to about 80°-85° C.beforehand. After vigorous stirring for 15 minutes, the mixture is leftto cool, with moderate stirring.

EXAMPLE 26 Day cream

This composition is identical to that of Example 25, the compound ofExample 6 being replaced by 0.8 g of the compound of Example 10.

EXAMPLE 27

    ______________________________________                                        Protecting milk                                                               ______________________________________                                        Compound of Example 8     0.5    g                                            Octyl p-dimethylaminobenzoate                                                                           0.5    g                                            Cetyl-stearyl alcohol     2      g                                            Cetyl alcohol             2      g                                            Triglycerides of C.sub.8 to C.sub.12 fatty acids                                                        20     g                                            Lanoline                  4      g                                            Stearic acid              0.5    g                                            Preservatives             0.3    g                                            Carbopol 934 (crosslinked polyacrylic                                                                   0.15   g                                            acid sold by GOODRICH CHEMICAL)                                               Triethanolamine           0.2    g                                            Perfume                   0.4    g                                            Demineralised water q.s.p.                                                                              100    g                                            ______________________________________                                    

The emulsion is prepared in the same way as in Example 25.

EXAMPLE 28

    ______________________________________                                        Oily-alcoholic sun lotion                                                     ______________________________________                                        Compound of Example 13    1.5    g                                            Perfume                   0.5    g                                            96° strength ethanol                                                                             47.5   g                                            Triglycerides of C.sub.8 to C.sub.12 fatty acids q.s.p.                                                 100    g                                            2-Ethylhexyl p-methoxycinnamate                                                                         2      g                                            ______________________________________                                    

The mixture of the various constituents is heated to about 40°-45° C. inorder to homogenise them and give a clear lotion.

EXAMPLE 29

    ______________________________________                                        Sun cream                                                                     ______________________________________                                        Compound of Example 8     3      g                                            4-[(2-Oxo-3-bornylidene)-methyl]-phenyl-                                                                2.5    g                                            trimethylammonium methylsulphate                                              Polyoxyethyleneated fatty alcohols                                                                      7      g                                            Triglycerides of C.sub.8 --C.sub.12 fatty acids                                                         30     g                                            Glycerol monostearate     2      g                                            Silicone oil              1.5    g                                            Cetyl alcohol             1.5    g                                            Preservatives             0.3    g                                            Perfume                   0.6    g                                            Demineralised water q.s.p.                                                                              100    g                                            ______________________________________                                    

The preparation of this cream is similar to that of Example 24; in thiscase, the 4-[(2-oxo-3-bornylidene)-methyl]-phenyltrimethylammoniummethylsulphate is dissolved in the water.

EXAMPLE 30

    ______________________________________                                        Sun cream                                                                     ______________________________________                                        Compound of Example 7    2.5    g                                             Benzylidene-camphor      4      g                                             Triglycerides of C.sub.8 to C.sub.12 fatty acids                                                       31     g                                             Glycerol monostearate    6      g                                             Stearic acid             2      g                                             Cetyl alcohol            1.2    g                                             Lanoline                 4      g                                             Preservatives            0.3    g                                             Propanediol              2      g                                             Triethanolamine          0.5    g                                             Perfume                  0.4    g                                             Demineralised water q.s.p.                                                                             100    g                                             ______________________________________                                    

The filters are dissolved in the fatty phase. The compound of Example 7can be replaced by 2.5 g of the compound of Example 11.

EXAMPLE 31 Sun oil

The following ingredients are mixed, if necessary with heating to40°-45° C. to homogenise them:

    ______________________________________                                        Compound of Example 8     3      g                                            Octyl p-dimethylaminobenzoate                                                                           3      g                                            Cacao butter              2.5    g                                            Antioxidants              0.05   g                                            Perfume                   0.5    g                                            Triglycerides of C.sub.8 to C.sub.12 fatty acids q.s.p.                                                 100    g                                            ______________________________________                                    

The compound of Example 8 can be replaced by 3 g of the compound ofExample 9.

EXAMPLE 32

    ______________________________________                                        Sun gel                                                                       ______________________________________                                        Compound of Example 5    2.5    g                                             2-Ethylhexyl p-methoxycinnamate                                                                        2.5    g                                             Cacao butter             5      g                                             Antioxidants             0.05   g                                             Silica                   10     g                                             Perfume                  0.5    g                                             Triglycerides q.s.p.     100    g                                             ______________________________________                                    

This fatty gel is prepared by heating the fatty substances to about40°-45° C. and then adding the silica, with vigorous stirring, and thefilters.

The same results are obtained by replacing the compound of Example 5 bythe compound of Example 3.

EXAMPLE 33

    ______________________________________                                        Sun milk                                                                      ______________________________________                                        Compound of Example 2     3      g                                            Compound of Example 14    2      g                                            Cetyl-stearyl alcohol     2      g                                            Cetyl alcohol             2      g                                            Triglycerides of C.sub.8 to C.sub.12 fatty acids                                                        20     g                                            Lanoline                  4      g                                            Stearic acid              0.5    g                                            Preservatives             0.3    g                                            Carbopol 934 (crosslinked polyacrylic                                                                   0.15   g                                            acid sold by GOODRICH CHEMICAL)                                               Triethanolamine           0.2    g                                            Demineralised water q.s.p.                                                                              100    g                                            ______________________________________                                    

This emulsion is prepared as in Example 25; the compound of Example 2 isdissolved in the aqueous phase, the compound of Example 14 beingdissolved in the fatty phase.

EXAMPLE 34

    ______________________________________                                        Aqueous-alcoholic sun gel                                                     ______________________________________                                        Carbopol 934               0.7    g                                           Triethanolamine            0.35   g                                           Propylene glycol           25     g                                           96° strength ethanol                                                                              25     g                                           Compound of Example 2      1      g                                           Diethanolamine salt of p-methoxycinnamic acid                                                            2.5    g                                           Preservative               0.3    g                                           Perfume                    0.4    g                                           Demineralised water q.s.p. 100    g                                           ______________________________________                                    

The carbopol is dispersed in the water with vigorous stirring and thetriethanolamine is then added, followed by the solvents and the water,in which the filters have been dissolved beforehand.

The same results are obtained by replacing the compound of Example 2 bythe compound of Example 4 in the form of the triethanolamine salt.

EXAMPLE 35

    ______________________________________                                        Sun cream                                                                     ______________________________________                                        Compound of Example 7     4      g                                            4-[(2-Oxo-3-bornylidene)-methyl]-phenyl-                                                                3.5    g                                            trimethylammonium methylsulphate                                                                        3.5    g                                            Polyoxyethyleneated fatty alcohols                                                                      7      g                                            Triglycerides of C.sub.8 to C.sub.12 fatty acids                                                        30     g                                            Glycerol monostearate     2      g                                            Silicone oil              1.5    g                                            Cetyl alcohol             1.5    g                                            Preservatives, perfume q.s.                                                   Demineralised water q.s.p.                                                                              100    g                                            ______________________________________                                    

The preparation of this cream is similar to that of Example 24, the4-[(2-oxo-3-bornylidene)-methyl]-phenyl-trimethylammonium methylsulphatebeing dissolved in the water.

The compound of Example 7 can be replaced by 2 g of the compound ofExample 12.

EXAMPLE 36

    ______________________________________                                        Sun cream                                                                     ______________________________________                                        Compound of Example 14     2      g                                           4'-Methoxy-4-tert.-butyldibenzoylmethane sold                                                            1      g                                           under the name PARSOL 1789 by GIVAUDAN                                        Polyoxyethyleneated fatty alcohols                                                                       7      g                                           Triglycerides of C.sub.8 to C.sub.12 fatty acids                                                         30     g                                           Glycerol monostearate      2      g                                           Silicone oil               1.5    g                                           Cetyl alcohol              1.5    g                                           Preservatives              0.4    g                                           Perfume                    0.5    g                                           Demineralised water q.s.p. 100    g                                           ______________________________________                                    

The compound of Example 14 and the Parsol 1789 are dissolved in thefatty phase.

EXAMPLES 37 TO 39

In these examples, the compounds of the formula (I) are used to protectcoloured compositions from the sun.

EXAMPLE 37

    ______________________________________                                        Coloured Shampoo                                                              ______________________________________                                        Triethanolamine lauryl-sulphate                                                                          10     g                                           0.05% strength solution of Orasol Blue BLW                                                               1      cc                                          Compound of Example 2      0.5    g                                           Perfume, preservative q.s.                                                    Water q.s.p.               100    g                                           ______________________________________                                    

EXAMPLE 38

    ______________________________________                                        Coloured shampoo                                                              ______________________________________                                        Triethanolamine lauryl-sulphate                                                                         10     g                                            Compound of Example 1     0.8    g                                            Fast Lilac W 5001 (Colour Index No. 45190)                                                              0.015  g                                            Perfume, preservative q.s.                                                    Water q.s.p.              100    g                                            ______________________________________                                    

EXAMPLE 39

    ______________________________________                                        Coloured setting lotion                                                       ______________________________________                                        Polyvinylpyrrolidone copolymer (of average                                                               2      g                                           molecular weight 40,000, sold under the code                                  K30 by GAF)                                                                   Fast Red CR1 W 3000 (Colour Index No. 27290)                                                             0.02   g                                           Compound of Example 3      0.3    g                                           96° strength ethanol                                                                              60     g                                           Water q.s.p.               100    g                                           ______________________________________                                    

These compositions do not change colour, even after exposure to the sunfor several weeks.

EXAMPLE 40 Sun oil

The following ingredients are mixed, if necessary with heating to40°-45° C. to homogenise them:

    ______________________________________                                        Compound of Example 15    3      g                                            Octyl p-dimethylaminobenzoate                                                                           3      g                                            Cacao butter              2.5    g                                            Antioxidants              0.05   g                                            Perfume                   0.5    g                                            Triglycerides of C.sub.8 to C.sub.12 fatty acids q.s.p.                                                 100    g                                            ______________________________________                                    

EXAMPLE 41

    ______________________________________                                        Aqueous-alcoholic sun gel                                                     ______________________________________                                        Carbopol 934            0.7    g                                              Triethanolamine         0.35   g                                              Propylene glycol        25     g                                              96° strength ethanol                                                                           25     g                                              Compound of Example 16  3      g                                              Preservative            0.3    g                                              Perfume                 0.4    g                                              Demineralised water q.s.p.                                                                            100    g                                              ______________________________________                                    

The carbopol is dispersed in the water with vigorous stirring and thetriethanolamine is then added, followed by the solvents and the water,in which the filter has been dissolved beforehand.

EXAMPLE 42

    ______________________________________                                        Sun cream                                                                     ______________________________________                                        Compound of Example 18   2.5    g                                             Benzylidene-camphor      4      g                                             Triglycerides of C.sub.8 to C.sub.12 fatty acids                                                       31     g                                             Glycerol monostearate    6      g                                             Stearic acid             2      g                                             Cetyl alcohol            1.2    g                                             Lanoline                 4      g                                             Preservatives            0.3    g                                             Propanediol              2      g                                             Triethanolamine          0.5    g                                             Perfume                  0.4    g                                             Demineralised water q.s.p.                                                                             100    g                                             ______________________________________                                    

The filters are dissolved in the fatty phase.

EXAMPLE 43

    ______________________________________                                        Sun milk                                                                      ______________________________________                                        Compound of Example 21    3      g                                            Benzylidene-camphor       2      g                                            Cetyl-stearyl alcohol     2      g                                            Cetyl alcohol             2      g                                            Triglycerides of C.sub.8 to C.sub.12 fatty acids                                                        20     g                                            Lanoline                  4      g                                            Stearic acid              0.5    g                                            Preservatives             0.3    g                                            Carbopol 934 (crosslinked polyacrylic                                                                   0.15   g                                            acid sold by GOODRICH CHEMICAL)                                               Triethanolamine           0.2    g                                            Demineralised water q.s.p.                                                                              100    g                                            ______________________________________                                    

This emulsion is prepared as in Example 33; the compound of Example 21is dissolved in the aqueous phase, the benzylidene-camphor beingdissolved in the fatty phase.

EXAMPLE 44

    ______________________________________                                        Moisturising face cream                                                       ______________________________________                                        Tween 60 = sorbitan monostearate oxyethyleneated                                                         1      g                                           with 20 mols of ethylene oxide, sold by ATLAS                                 Cetyl alcohol              1      g                                           Perhydrosqualene           10     g                                           Virgin sesame oil          5      g                                           Stearic acid               2      g                                           Glycerol                   3      g                                           Compound of Example 20     1      g                                           Methyl para-hydroxybenzoate                                                                              0.3    g                                           Perfume                    0.3    g                                           Water q.s.p.               100    g                                           ______________________________________                                    

EXAMPLE 45

    ______________________________________                                        Protecting and moisturising fluid body emulsion                               ______________________________________                                        Myrj 49 = polyethylene glycol stearate sold                                                              0.8    g                                           by ATLAS                                                                      Self-emulsifiable glycerol stearate                                                                      1.2    g                                           Stearyl alcohol            1      g                                           Vaseline oil               8      g                                           Soya oil                   3      g                                           Amerchol L 101 = extract of sterols and complex                                                          3      g                                           higher alcohols of lanoline, in their free form,                              sold by AMERCHOL                                                              Compound of Example 20     1.5    g                                           Methyl para-hydroxybenzoate                                                                              0.3    g                                           Perfume                    0.3    g                                           Water q.s.p.               100    g                                           ______________________________________                                    

EXAMPLE 46

    ______________________________________                                        Moisturising hand cream                                                       ______________________________________                                        Brij 56 = cetyl alcohol oxyethyleneated with                                                             2      g                                           10 mols of ethylene oxide, sold by ATLAS                                      Self-emulsifiable glycerol stearate                                                                      2      g                                           Cetyl alcohol              1      g                                           Vaseline oil               5      g                                           Isopropyl myristate        5      g                                           Lanoline                   3      g                                           Compound of Example 20     2      g                                           Methyl para-hydroxybenzoate                                                                              0.3    g                                           Perfume                    0.3    g                                           Water q.s.p.               100    g                                           ______________________________________                                    

EXAMPLE 47

    ______________________________________                                        Stimulating cream                                                             ______________________________________                                        Germal 115 = imidazoline/urea copolymer sold                                                             0.3    g                                           by SUTTON LARS                                                                Compound of Example 20     1      g                                           Omadine MDS = 2,2'-bis-N--hydroxypyridyl                                                                 0.025  g                                           disulphide/magnesium sulphate complex sold by                                 OLIN                                                                          Triethanolamine            0.5    g                                           Cetiol LC = cetyl laurate sold by HENKEL                                                                 1      g                                           Rutile titanium oxide      0.5    g                                           Triple pressed stearine    3      g                                           Mixture of glycerol monostearate and distearate                                                          3      g                                           Double-distilled pure cetyl alcohol                                                                      3      g                                           Nesatol = triglycerides of C.sub.10 --C.sub.18 fatty                                                     1      g                                           acids, sold by VEVY                                                           Calophyllum oil            0.5    g                                           BHA = butylhydroxyanisole  0.03   g                                           Nipa ester 82121 = mixture of methyl, ethyl,                                                             0.2    g                                           propyl, butyl and benzyl para-hydroxybenzoates                                Talc                       3      g                                           Octyl p-dimethylaminobenzoate                                                                            1.5    g                                           Perfume                    0.4    g                                           Demineralised water q.s.p. 100    g                                           ______________________________________                                    

EXAMPLE 48

    ______________________________________                                        Sun oil                                                                       ______________________________________                                        Compound of Example 22    1.5    g                                            Compound of Example 23    1.5    g                                            Cacao butter              2.5    g                                            Antioxidants              0.05   g                                            Perfume                   0.5    g                                            Triglycerides of C.sub.8 --C.sub.12 fatty acids q.s.p.                                                  100    g                                            ______________________________________                                    

We claim:
 1. 3-Benzylidene-camphor derivative having the generalformula: ##STR38## in which R₁ denotes a hydrogen atom or the radicalSO₃.sup.⊖ M.sup.⊕, in which M is hydrogen, an alkali metal or the groupN.sup.⊕ (R₃)₄, each R₃ independently denoting hydrogen or a C₁ to C₄alkyl or hydroxyalkyl group; R₂ denotes a linear or branched C₁ to C₄alkyl radical or a C₁ to C₄ alkoxy radical, n being 0 or an integer from1 to 4 such that when n is 2 or more the R₂ radicals can be the same ordifferent; and Z represents a group of the formula: ##STR39## in whichR₅ denotes a hydrogen atom, a C₁ to C₄ alkyl radical, an aryl radical,an aryl radical substituted by one or more halogen atoms or by C₁ to C₄alkyl or alkoxy groups, or a radical ##STR40## and R₆ denotes a radical--COOR₈ or ##STR41## in which R₇ and R₈, which are identical ordifferent, denote a substituted or unsubstituted alkyl, alkenyl,cycloalkyl or aralkyl radical containing up to 20 carbon atoms, whichsubstituent is one or more hydroxyl, alkoxy, amine or quaternaryammonium groups, and R₉ and R₁₀, which are identical or different,denote a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl,cycloalkyl or aralkyl radical containing up to 20 carbon atoms, whichsubstituent is one or more hydroxyl, alkoxy, amine or quaternaryammonium groups, or, alternatively, if R₅ denotes a hydrogen atom, analkyl radical or a substituted or unsubstituted aryl radical, R₆ canalso represent a radical --COO.sup.⊕ M.sup.⊖, M being defined as above,with the proviso that the methylidene-camphor radical and the radical Z,which are attached to the aromatic nucleus A, are either in the metaposition or in the para position relative to one another.
 2. Aderivative according to claim 1 which has the formula ##STR42## in whichR₁ denotes a hydrogen atom and Z represents a group of the formula##STR43##
 3. A derivative according to claim 1 which has the formula:##STR44## in which Z represents the group --CH═CH--CO₂ ethyl.
 4. Processfor the preparation of a compound as claimed in claim 1 in which Zrepresents a group: ##STR45## which comprises reacting a 3'- or4'-formyl-3-benzylidene-camphor of the formula: ##STR46## in which R₁and R₂ are as defined in claim 1, with a malonic acid derivative of theformula: ##STR47##
 5. A composition suitable for cosmetic use whichcontains at least one 3-benzylidene-camphor derivative as defined inclaim
 1. 6. A composition which contains at least one derivative asclaimed in claim
 2. 7. A composition according to claim 5, in which thederivative is present in an amount from 0.5 to 15% by weight, relativeto the total weight of the composition.
 8. A composition according toclaim 5, which contains at least one cosmetic adjuvant which is athickener, softener, superfatting agent, emollient, humectant, wettingagent, surface-active agent, preservative, anti-foam agent, perfume,oil, wax, dyestuff or pigment.
 9. A composition according to claim 5,which is in the form of an anti-sunburn composition and contains atleast one derivative as claimed in claim 1 associated with anotherwater-soluble or liposoluble sun filter having a filtering action withrespect to UV-B rays, or with another sun filter which filters out theUV-A rays.
 10. A composition according to claim 9 in which the said sunfilter having a filtering action with respect to UV-B rays is a camphorderivative, coffee bean oil, salicylic acid derivative, cinnamic acidderivative, p-aminobenzoic acid derivative or benzophenone derivative.11. A composition according to claim 9 in which the said sun filterwhich filters out UV-A rays is a dibenzoylmethane derivative.
 12. Acomposition according to claim 5, which is in the form of a coloured ornon-coloured cosmetic composition stabilised to light and is a hairlacquer, a setting lotion, a shampoo, a colouring shampoo or a hairdyeing composition, a nail varnish, a lipstick, an epidermis treatmentcream or a make-up foundation.
 13. Process for protecting the humanepidermis against UV-A and/or UV-B rays, which comprises applyingthereto at least one derivative as defined in claim
 1. 14. Process forprotecting a coloured cosmetic composition against UV radiation, whichcomprises incorporating therein at least one derivative as defined inclaim 1.